CN112774459A - Calcium carbonate in-situ polymerization PVC hollow fiber ultrafiltration membrane and preparation method thereof - Google Patents
Calcium carbonate in-situ polymerization PVC hollow fiber ultrafiltration membrane and preparation method thereof Download PDFInfo
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- CN112774459A CN112774459A CN202011509280.0A CN202011509280A CN112774459A CN 112774459 A CN112774459 A CN 112774459A CN 202011509280 A CN202011509280 A CN 202011509280A CN 112774459 A CN112774459 A CN 112774459A
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- calcium carbonate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
Abstract
The invention provides a calcium carbonate in-situ polymerization PVC hollow fiber ultrafiltration membrane and a preparation method thereof, wherein the method comprises the following steps: the preparation method comprises the steps of firstly preparing a nano calcium carbonate dispersing agent, then preparing graphene in-situ polymerization PVC by using a vinyl chloride monomer, a calcium carbonate dispersing agent, an initiator, a stabilizer and the like, mixing the graphene in-situ polymerization PVC with a solvent, an additive and the like to prepare a membrane casting solution, and spinning by using a dry-wet method to obtain a modified PVC hollow fiber ultrafiltration membrane.
Description
Technical Field
The invention relates to the technical field of water treatment equipment, in particular to a calcium carbonate in-situ polymerization PVC hollow fiber ultrafiltration membrane and a preparation method thereof.
Background
At present, the mainstream ultrafiltration membrane materials mainly comprise polyvinyl chloride, polyether sulfone, polysulfone, polyvinylidene fluoride and the like, wherein the polyvinyl chloride ultrafiltration membrane has the lowest cost and the most extensive market application and can meet the requirements of most production and application, but the polyvinyl chloride ultrafiltration membrane has many defects, the temperature resistance of the polyvinyl chloride is general, the service temperature of a finished polyvinyl chloride membrane component cannot exceed 45 ℃, and if the polyvinyl chloride membrane component works in an environment higher than 45 ℃ for a long time, the membrane performance is influenced, such as the reduction of mechanical strength, the reduction of water flux and the like.
In view of the above, a solution for improving a polyvinyl chloride ultrafiltration membrane to improve the high temperature resistance of polyvinyl chloride is needed.
Disclosure of Invention
In view of the above, the invention provides a high-temperature-resistant calcium carbonate in-situ polymerization PVC hollow fiber ultrafiltration membrane and a preparation method thereof.
The technical scheme of the invention is realized in such a way that the invention provides a preparation method of a calcium carbonate in-situ polymerization PVC hollow fiber ultrafiltration membrane, which comprises the following steps:
step one, preparing calcium carbonate in-situ polymerized PVC, respectively putting a vinyl chloride monomer, nano calcium carbonate, a dispersing agent, an initiator and a stabilizing agent into a reaction kettle, controlling the reaction temperature to be 55-65 ℃ and the pressure to be 0.7-0.8MPa, reacting for 10-14h, and washing and drying to obtain the calcium carbonate in-situ polymerized PVC;
step two, preparing a membrane casting solution, namely respectively putting calcium carbonate in-situ polymerization PVC, a solvent and an additive into a reaction kettle, controlling the reaction temperature to be 45-50 ℃, stirring and reacting for 12-17h under normal pressure at the stirring speed of 150-160r/min, and standing for 1-3h after the reaction is finished to obtain the membrane casting solution;
and step three, preparing membrane wires, namely extruding the membrane casting solution through a spray head, performing phase inversion through a coagulating bath to form a membrane, sequentially passing through a pickling tank and a rinsing tank, and then rolling to obtain the calcium carbonate in-situ polymerization PVC hollow fiber ultrafiltration membrane.
On the basis of the above technical scheme, preferably, in the step one, the mass ratio of the vinyl chloride monomer, the nano calcium carbonate, the dispersing agent, the initiator and the stabilizing agent is (70-80): (5-10): (10-20): (1-2): (0.1-0.5).
On the basis of the technical scheme, the average particle size of the nano calcium carbonate is preferably 30-50 nm.
On the basis of the above technical solution, preferably, the dispersant is polyvinyl alcohol or hydroxypropyl methylcellulose, the initiator is bis (2-ethylhexyl) peroxydicarbonate, and the stabilizer is dioctyltin.
More preferably, in the second step, the mass ratio of the calcium carbonate in-situ polymerized PVC to the solvent to the additive is (15-20): (65-80): (5-15).
On the basis of the above technical solution, preferably, in the second step, the solvent is one or a mixture of several of DMAC, DMF, and NMP, and the additive is one or a mixture of several of PEG400, PEG800, PVP (K30), and PVP (K90).
On the basis of the above technical solution, preferably, in the third step, the coagulation bath is pure water, and the temperature of the coagulation bath is 30 ℃.
Based on the above technical scheme, preferably, in the third step, the pickling tank is 1 (wt)% of citric acid aqueous solution.
On the basis of the above technical scheme, preferably, in the third step, the water washing tank is filled with pure water, and the temperature of the pure water in the water washing tank is 45 ℃.
On the basis of the technical scheme, preferably, in the step three, the retention time in the coagulating bath is 10-20s, the retention time in the pickling tank is 30-50s, and the retention time in the rinsing tank is 30-50 s.
The invention also discloses the calcium carbonate in-situ polymerization PVC hollow fiber membrane prepared by the preparation method.
Compared with the prior art, the calcium carbonate in-situ polymerization PVC hollow fiber ultrafiltration membrane and the preparation method thereof have the following beneficial effects:
(1) according to the calcium carbonate in-situ polymerization PVC hollow fiber ultrafiltration membrane, the PVC is subjected to in-situ polymerization modification by adopting the nano calcium carbonate, the polymerization performance of the modified PVC hollow fiber ultrafiltration membrane is improved, the problem that the conventional PVC hollow fiber membrane cannot resist high temperature is solved, and meanwhile, the water flux of the hollow fiber membrane is greatly improved;
(2) according to the invention, the formula of the membrane casting solution is improved, the calcium carbonate in-situ polymerization PVC is prepared by utilizing the nano calcium carbonate, the dispersing agent, the initiator and the vinyl chloride monomer, then the membrane casting solution is prepared, the membrane casting solution is spun by adopting a dry-wet method to prepare the ultrafiltration membrane, the overall method is simple, the performance of the PVC hollow fiber membrane is greatly improved by improving the raw materials and the process, and the application prospect is good.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
Respectively weighing 70kg of vinyl chloride monomer, 5kg of nano calcium carbonate with the average particle size of 30nm, 10kg of polyvinyl alcohol, 1kg of bis (2-ethylhexyl) peroxydicarbonate and 0.1kg of dioctyltin, sequentially putting the materials into a reaction kettle, controlling the reaction temperature to be 55 ℃ and the pressure in the kettle to be 0.7MPa, stirring for 10 hours, after the reaction is finished, adding 100kg of water for 3 times, stirring, cleaning, layering and finishing cleaning to obtain the in-situ polymerized PVC resin.
And weighing 15kg of in-situ polymerization PVC resin, 65kgDMAC and 5kgPEG400, sequentially adding into a reaction kettle, controlling the temperature in the reaction kettle to be 45 ℃, stirring and reacting for 12 hours under normal pressure at the stirring speed of 150r/min, and standing for 1 hour after the reaction is finished to obtain the membrane casting solution.
Extruding the casting membrane liquid through a spray head, carrying out membrane forming treatment in a water bath, wherein the retention time of the water bath is 10s, then sequentially carrying out acid washing for 30s and water washing for 30s, and rolling to obtain the hollow fiber ultrafiltration membrane wire with the inner diameter of 0.9mm and the outer diameter of 1.6mm, wherein pure water is used in the water bath, the temperature of the water bath is 30 ℃, 1 (wt)% of citric acid aqueous solution is used in a pickling bath, and pure water with the temperature of 45 ℃ is used in a washing bath.
Example 2
Respectively weighing 72kg of vinyl chloride monomer, 6kg of nano calcium carbonate with the average particle size of 35nm, 12kg of polyvinyl alcohol, 1.2kg of bis (2-ethylhexyl) peroxydicarbonate and 0.2kg of dioctyltin, sequentially putting the materials into a reaction kettle, controlling the reaction temperature to be 58 ℃ and the pressure in the kettle to be 0.7MPa, stirring and reacting for 11 hours, adding 100kg of water for 3 times after the reaction is finished, stirring, cleaning, layering, and cleaning to obtain the in-situ polymerized PVC resin.
And weighing 16kg of in-situ polymerization PVC resin, 74kg of DMF and 7kg of PEG800, sequentially adding into a reaction kettle, controlling the temperature in the reaction kettle to be 46 ℃, stirring and reacting for 13 hours under normal pressure at the stirring speed of 150r/min, standing for 2 hours after the reaction is finished, and obtaining the membrane casting solution.
Extruding the casting membrane liquid through a spray head, carrying out membrane forming treatment in a water bath, wherein the retention time of the water bath is 13s, then carrying out acid washing for 33s and water washing for 33s in sequence, and rolling to obtain the hollow fiber ultrafiltration membrane wire with the inner diameter of 0.9mm and the outer diameter of 1.6mm, wherein the water bath uses pure water, the temperature of the water bath is 30 ℃, the pickling bath contains 1 (wt)% of citric acid aqueous solution, and the washing bath contains 45 ℃ pure water.
Example 3
Respectively weighing 75kg of vinyl chloride monomer, 8kg of nano calcium carbonate with the average particle size of 40nm, 20kg of polyvinyl alcohol, 1.5kg of bis (2-ethylhexyl) peroxydicarbonate and 0.5kg of dioctyltin, sequentially putting the materials into a reaction kettle, controlling the reaction temperature to be 60 ℃ and the pressure in the kettle to be 0.8MPa, stirring and reacting for 12 hours, adding 100kg of water for 3 times after the reaction is finished, stirring, cleaning, layering, and cleaning to obtain the in-situ polymerized PVC resin.
And then weighing 18kg of in-situ polymerization PVC resin, 69kg of NMP and 13kg of PVP (K30), sequentially putting into a reaction kettle, controlling the temperature in the reaction kettle to be 47 ℃, stirring and reacting for 14 hours under normal pressure at the stirring speed of 160r/min, and standing for 2 hours after the reaction is finished to obtain the membrane casting solution.
Extruding the casting membrane liquid through a spray head, carrying out membrane forming treatment in a water bath, wherein the retention time of the water bath is 15s, then sequentially carrying out acid washing for 35s and water washing for 35s, and rolling to obtain the hollow fiber ultrafiltration membrane wire with the inner diameter of 0.9mm and the outer diameter of 1.6mm, wherein the water bath uses pure water, the temperature of the water bath is 30 ℃, the pickling bath contains 1 (wt)% of citric acid aqueous solution, and the washing bath contains 45 ℃ pure water.
Example 4
Respectively weighing 78kg of vinyl chloride monomer, 7kg of nano calcium carbonate with the average particle size of 45nm, 14kg of hydroxypropyl methyl cellulose, 1.8kg of bis (2-ethylhexyl) peroxydicarbonate and 0.3kg of dioctyltin, sequentially putting the materials into a reaction kettle, controlling the reaction temperature to be 63 ℃ and the pressure in the kettle to be 0.8MPa, stirring and reacting for 13 hours, adding 100kg of water for 3 times after the reaction is finished, stirring, cleaning, layering and cleaning to obtain the in-situ polymerized PVC resin.
And weighing 17kg of in-situ polymerization PVC resin, 46kg of DMAC, 30kg of DMF and 9kg of PVP (K90), sequentially putting into a reaction kettle, controlling the temperature in the reaction kettle to be 48 ℃, stirring and reacting for 15h under normal pressure at the stirring speed of 160r/min, standing for 3h after the reaction is finished, and obtaining the casting solution.
Extruding the casting membrane liquid through a spray head, carrying out membrane forming treatment in a water bath, wherein the retention time of the water bath is 17s, then carrying out acid washing for 37s and water washing for 37s in sequence, and rolling to obtain the hollow fiber ultrafiltration membrane wire with the inner diameter of 0.9mm and the outer diameter of 1.6mm, wherein pure water is used in the water bath, the temperature of the water bath is 30 ℃, 1 (wt)% of citric acid aqueous solution is used in a pickling bath, and pure water with the temperature of 45 ℃ is used in a washing bath.
Example 5
Respectively weighing 80kg of vinyl chloride monomer, 10kg of nano calcium carbonate with the average particle size of 50nm, 16kg of hydroxypropyl methyl cellulose, 2kg of bis (2-ethylhexyl) peroxydicarbonate and 0.4kg of dioctyltin, sequentially putting the materials into a reaction kettle, controlling the reaction temperature to be 65 ℃ and the pressure in the kettle to be 0.7MPa, stirring and reacting for 14h, adding 100kg of water for 3 times after the reaction is finished, stirring, cleaning, layering, and cleaning to obtain the in-situ polymerized PVC resin.
And then weighing 20kg of in-situ polymerization PVC resin, 40kg of DMF, 40kg of NMP, 10kg of PEG400 and 5kg of PVP (K30), sequentially putting into a reaction kettle, controlling the temperature in the reaction kettle to be 50 ℃, stirring at normal pressure for reaction for 17 hours, controlling the stirring speed to be 160r/min, standing for 3 hours after the reaction is finished, and obtaining the casting solution.
Extruding the casting membrane liquid through a spray head, carrying out membrane forming treatment in a water bath, wherein the retention time of the water bath is 20s, then sequentially carrying out acid washing for 40s and water washing for 40s, and rolling to obtain the hollow fiber ultrafiltration membrane wire with the inner diameter of 0.9mm and the outer diameter of 1.6mm, wherein the water bath uses pure water, the temperature of the water bath is 30 ℃, the pickling bath contains 1 (wt)% of citric acid aqueous solution, and the washing bath contains 45 ℃ pure water.
Comparative example
Respectively weighing 18kg of PVC resin, 69kg of DMAC, 10kg of PEG400 and 3kg of PVP (K30), sequentially putting into a reaction kettle, controlling the temperature to 47 ℃, stirring and reacting for 15h under normal pressure at the stirring speed of 150r/min, standing for 2h after the reaction is finished, and obtaining the membrane casting solution.
Extruding the casting solution through a spray head, performing film forming treatment in a water bath for 15s, sequentially passing through a pickling tank for 40s and a rinsing tank for 45s to obtain the hollow fiber ultrafiltration membrane wire with the inner diameter of 0.9mm and the outer diameter of 1.6mm, wherein the water bath adopts pure water, the temperature of the water bath is 30 ℃, the temperature of the water bath is 1 (wt)% of citric acid aqueous solution in the pickling tank, and the temperature of the water bath is 45 ℃.
The ultrafiltration membrane filaments obtained in the above examples 1 to 5 and comparative examples were subjected to performance tests, and the ultrafiltration membrane filaments obtained in the examples and comparative examples were respectively subjected to 48 hours of operation at 25 ℃, 45 ℃ and 60 ℃, and then the breaking tension, the contact angle and the pure water flux were measured, and the results were as follows:
the ultrafiltration membrane filaments of examples 1-5 and comparative example were run at 25 ℃ for 48h with the following test results:
the ultrafiltration membrane filaments of examples 1-5 and comparative example were run at 45 ℃ for 48h with the following test results:
| detecting items | Breaking tension | Contact angle | Pure water flux |
| Example 1 | 8.1N | 46° | 490L/(m2·h) |
| Example 2 | 8.1N | 45° | 480L/(m2·h) |
| Example 3 | 8.2N | 45° | 490L/(m2·h) |
| Example 4 | 8.1N | 45° | 490L/(m2·h) |
| Example 5 | 8.2N | 45° | 480L/(m2·h) |
| Comparative example | 5.5N | 58° | 320L/(m2·h) |
The ultrafiltration membrane filaments of examples 1-5 and comparative example were run at 60 ℃ for 48h with the following test results:
| detecting items | Breaking tension | Contact angle | Pure water flux |
| Example 1 | 8.1N | 47° | 470L/(m2·h) |
| Example 2 | 8.1N | 46° | 480L/(m2·h) |
| Example 3 | 8.0N | 46° | 470L/(m2·h) |
| Example 4 | 8.1N | 46° | 470L/(m2·h) |
| Example 5 | 8.0N | 47° | 470L/(m2·h) |
| Comparative example | 3.2N | 62° | 180L/(m2·h) |
The data show that the calcium carbonate in-situ polymerization PVC hollow fiber ultrafiltration membrane prepared by the preparation method has good high temperature resistance, has better mechanical strength and water flux compared with the conventional PVC hollow fiber ultrafiltration membrane, and still has good mechanical property and water flux when working in a high-temperature environment.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a calcium carbonate in-situ polymerization PVC hollow fiber ultrafiltration membrane is characterized by comprising the following steps:
step one, preparing calcium carbonate in-situ polymerized PVC, respectively putting a vinyl chloride monomer, nano calcium carbonate, a dispersing agent, an initiator and a stabilizing agent into a reaction kettle, controlling the reaction temperature to be 55-65 ℃ and the pressure to be 0.7-0.8MPa, reacting for 10-14h, and washing and drying to obtain the calcium carbonate in-situ polymerized PVC;
step two, preparing a membrane casting solution, namely respectively putting calcium carbonate in-situ polymerization PVC, a solvent and an additive into a reaction kettle, controlling the reaction temperature to be 45-50 ℃, stirring and reacting for 12-17h under normal pressure at the stirring speed of 150-160r/min, and standing for 1-3h after the reaction is finished to obtain the membrane casting solution;
and step three, preparing membrane wires, namely extruding the membrane casting solution through a spray head, performing phase inversion through a coagulating bath to form a membrane, sequentially passing through a pickling tank and a rinsing tank, and then rolling to obtain the calcium carbonate in-situ polymerization PVC hollow fiber ultrafiltration membrane.
2. The preparation method of the calcium carbonate in-situ polymerization PVC hollow fiber ultrafiltration membrane according to claim 1, wherein in the first step, the mass ratio of the vinyl chloride monomer, the nano calcium carbonate, the dispersing agent, the initiator and the stabilizing agent is (70-80): (5-10): (10-20): (1-2): (0.1-0.5).
3. The preparation method of the calcium carbonate in-situ polymerization PVC hollow fiber ultrafiltration membrane according to claim 1, wherein the average particle size of the nano calcium carbonate is 30-50 nm.
4. The method for preparing the calcium carbonate in-situ polymerization PVC hollow fiber ultrafiltration membrane according to claim 1, wherein the dispersing agent is polyvinyl alcohol or hydroxypropyl methyl cellulose, the initiator is bis (2-ethylhexyl) peroxydicarbonate, and the stabilizing agent is dioctyltin.
5. The preparation method of the calcium carbonate in-situ polymerization PVC hollow fiber ultrafiltration membrane according to claim 1, wherein in the second step, the mass ratio of the calcium carbonate in-situ polymerization PVC, the solvent and the additive is (15-20): (65-80): (5-15).
6. The method for preparing the calcium carbonate in-situ polymerization PVC hollow fiber ultrafiltration membrane according to claim 1, wherein in the second step, the solvent is one or a mixture of several of DMAC, DMF and NMP, and the additive is one or a mixture of several of PEG400, PEG800, PVP (K30) and PVP (K90).
7. The method for preparing the calcium carbonate in-situ polymerization PVC hollow fiber ultrafiltration membrane according to claim 1, wherein in the third step, the coagulation bath is pure water, and the temperature of the coagulation bath is 30 ℃.
8. The method for preparing the calcium carbonate in-situ polymerization PVC hollow fiber ultrafiltration membrane according to claim 1, wherein in the third step, the pickling tank is 1 (wt)% of citric acid aqueous solution.
9. The preparation method of the calcium carbonate in-situ polymerization PVC hollow fiber ultrafiltration membrane as claimed in claim 1, wherein in the third step, the water washing tank is filled with pure water, and the temperature of the pure water in the water washing tank is 45 ℃.
10. The method for preparing the calcium carbonate in-situ polymerization PVC hollow fiber ultrafiltration membrane as claimed in claim 1, wherein in the third step, the residence time in the coagulation bath is 10-20s, the residence time in the pickling tank is 30-50s, and the residence time in the rinsing tank is 30-50 s.
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Citations (5)
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| CN1468901A (en) * | 2003-06-24 | 2004-01-21 | 新疆石河子中发化工有限责任公司 | Comprehensive dispersing technology for in-situ polymerization of nano calcium carbonate modified PVC resin |
| CN101912739A (en) * | 2010-08-18 | 2010-12-15 | 天津工业大学 | Preparation method of polyvinyl chloride hollow-fiber membrane |
| CN104587843A (en) * | 2015-01-27 | 2015-05-06 | 新疆艾美环保科技有限公司 | Preparation process of hollow fiber membranes |
| CN105693900A (en) * | 2016-04-08 | 2016-06-22 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Preparation method of nano calcium carbonate/vinyl chloride in-situ polymerization composite resin |
| CN106582309A (en) * | 2016-12-30 | 2017-04-26 | 汕头高新区嘉逸包装技术有限公司 | Forming process of hollow fiber membrane |
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2020
- 2020-12-18 CN CN202011509280.0A patent/CN112774459A/en active Pending
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| CN1468901A (en) * | 2003-06-24 | 2004-01-21 | 新疆石河子中发化工有限责任公司 | Comprehensive dispersing technology for in-situ polymerization of nano calcium carbonate modified PVC resin |
| CN101912739A (en) * | 2010-08-18 | 2010-12-15 | 天津工业大学 | Preparation method of polyvinyl chloride hollow-fiber membrane |
| CN104587843A (en) * | 2015-01-27 | 2015-05-06 | 新疆艾美环保科技有限公司 | Preparation process of hollow fiber membranes |
| CN105693900A (en) * | 2016-04-08 | 2016-06-22 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Preparation method of nano calcium carbonate/vinyl chloride in-situ polymerization composite resin |
| CN106582309A (en) * | 2016-12-30 | 2017-04-26 | 汕头高新区嘉逸包装技术有限公司 | Forming process of hollow fiber membrane |
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